CN102387988A

CN102387988A - A process for manufacturing phosphaorous trichloride phosphorous pentachloride and cement

Info

Publication number: CN102387988A
Application number: CN2009801547821A
Authority: CN
Inventors: 凯西·H.·哈达
Original assignee: Individual
Current assignee: Individual
Priority date: 2008-12-11
Filing date: 2009-12-11
Publication date: 2012-03-21
Also published as: EP2370352A2; US9199878B2; US20110256040A1; WO2010084509A4; WO2010084509A2; EP2370352B1; WO2010084509A3

Abstract

A process for manufacturing phosphorous trichloride, phosphorous pentachloride and cement comprising of heating at elevated temperature of 1 100 DEG C to 1500 DEG C pulverised mixture of phosphate ores, carbonaceous substances, silica and/or alumina and treating the resultant gaseous products with chlorine in the ratio of 1 to 5 moles of chlorine per mole of phosphorous oxide contained in the phosphate ores while maintaining the temperature between 400 DEG C to 1000 DEG C by cooling and thereafter firstly separating gaseous mixture of primarily phosphorous trichloride and phosphorous pentachloride, from cement and later separating phosphorous trichloride and phosphorous pentachloride, both separations by known methods.

Description

A kind of method for preparing phosphorus trichloride, phosphorus pentachloride and cement

Brief introduction

The present invention relates to a kind ofly produce phosphorus trichloride, phosphorous pentachloride and such as the novel process of cement commonly used such as silicate cement.This technology is handled the phosphorus ore of different mass fully, and the method for employing is: directly phosphorus content is converted into except cement commonly used and also is included in commercial significant phosphorus trichloride and phosphorous pentachloride.This method can not reduce its element form.

Phosphorus is a kind of important element; In fertilizer, agrochemicals, animal-feed, plastics and general chemical, has very wide industrial application; Affect human happiness in many aspects, therefore, any improvement in manufacturing processed all must promote the well-being of mankind greatly.

The present invention not only makes the production technique of phosphorus chloride simple, direct, economical, also can other reject products be converted into cement commonly used of equal importance (being used for building), thereby have multiple benefit.

Background technology

USP 1730521 has been introduced through in phosphorus ore, being mixed into SiO2 and carrying out heat together, calcium and SiO2 amount is converted into calcium-silicate (using coke as thermal energy source) carries out phosphorus chloride production with chlorine.

USP 3241917 in 1962 has been introduced a kind of technology of handling phosphorus ore production P2O5 through the coke gasification reaction device.

USP 3247014 has been described a kind of fluidized-bed reactor.This reactor drum uses the CO plasma heating, produces the calcium-silicate slag.

The U.S. 3723608 has described a kind of through electrically heated mode, produces the technology of phosphorus with phosphorus ore, silicon-dioxide and C.

USP 3923961 has been introduced and a kind ofly in rotary kiln, has been produced the technology of phosphorus and tricalcium orthophosphate through adding or do not add silicon-dioxide.

USP 4389384 has been introduced a kind of carbonaceous thing and silicon-dioxide reduction Rock Phosphate (72Min BPL), the technology of oxidation step as P2O5 of going forward side by side used.

USP 4351813 has been told about a kind of technology that adopts phosphorus ore to produce P2O5 or phosphorus or phosphoric acid.

USP 3235330 has been introduced through going back phosphorus (Al2O3 and the SiO2 that in residue, add various amounts form cement clinker) recovery phosphorus and the cement clinker from phosphorus ore that raw calcium phosphate and in-situ oxidation produce.

Above-mentioned these technologies all can't be favored and receive phosphorus-phosphorus derivant industry as the technology of viable commercial.Phosphorus already adopts the important process of electric arc furnace technology as commercial system phosphorus, and its verivate of utilization phosphorus production, like PCl3, PCl5, P2O5, P2S5 and phosphoric acid.This technology will lose calcium constituent in the Calucium Silicate powder, and consume a large amount of electric power.Said technology can be summarized as follows:

Phosphate rock is polished in ball mill usually and is granulated, and uses clay to typically have a diameter from 1 centimetre agglomerate or granule with formation as tackiness agent.Any particulate that produces in the downstream process or broken granule all reclaim and recycling at this point.In order to reinforce, it is cured in stove, to form solid mass, this stove uses in the downstream process stage usually and as the carbon monoxide that sub product produces fuel is provided.This step will be carried out under sufficiently high temperature, guarantees that fluorochemical contained in the granule is along with stove waste gas is dispersed.Be transported in the phosphorus stove large-scale bunker on one side with the granule cooling and with it subsequently.There, together constantly be fed in the stove together with an amount of carbon (being generally coke) and silicon-dioxide stream through gravity.

The phosphorus stove is originally also original design as the lining carbon electric arc, passes bell and is hanging many carbon dioxide process carbon electrodes, and these electrodes maintain the drop-bottom top.Energy expenditure receives the conductivity influence of physics load, can be through raising or reduce the electrode red-tape operati temperature of suspension, so that energy expenditure maintained the level of an anticipation.Usually should be with temperature maintenance at 1200 ℃-1500 ℃.

A large amount of (in the phosphorus per ton of generation up to the 7-8MT) Calucium Silicate powder (CaSiO3) that generates as sub product is in the fusion stage, is accumulated in the drop-bottom place.Regularly with its taking-up and transfer in the outside hole, be cooled to hard bulk there, can this blocks be pulverized and be used for selling or being used for construction industry as slag.

Should consequent phosphorus be converted into PCl3 or other compounds, once more consumed energy in different devices.

Invention

According to the present invention, can use a kind of comprehensive, ECO-friendly, economic mode to process phosphorus ore, use a kind of standard equipment that simply can make up to produce phosphorus chloride neatly, need not to use a large amount of rare electric power, will not be reduced to element phosphor by phosphoric acid salt.

The present invention proposes a kind of method for preparing phosphorus trichloride, phosphorous pentachloride and cement commonly used; Comprise: the powder mixture that uses 1100 ℃ to 1500 ℃ heat phosphorus ore, carbonaceous thing, silicon-dioxide and/or aluminum oxide; Use chlorine to handle the synthesis gas product, through cooling temperature is remained on 400 ℃ to 1000 ℃ simultaneously, wherein; The molar ratio of contained phosphorous oxides is 1: 5 in chlorine and the phosphorus ore; At first the gaseous mixture of phosphorus trichloride and phosphorous pentachloride (as there be too much Cl2, when cooling contain the PCl3 of this gas form) with commonly used cement separated thereafter; Secondly phosphorus trichloride is separated with phosphorous pentachloride, twice separation all adopts currently known methods to carry out.Any or multiple in the preferred coke of above-mentioned carbonaceous thing, semicoke, pitch, charcoal or the biomass C.In above-mentioned technology, phosphorus ore preferably contains 2% to 45% phosphorous oxides, preferably in the mixture of phosphorus ore, carbonaceous thing, silicon-dioxide and/or aluminum oxide, adds red stone.

The special feature of the inventive method is, method is quite flexible, because except phosphorus chloride, the verivate of phosphorus (for example P2O5, P2S5 and phosphoric acid) also can adopt heating/cooling operation to produce arbitrarily with any ratio through the input amount of control chlorine or its compound.Wherein, phosphorus ore can with together heating at high temperature such as the SiO2 of forms such as a certain amount of, clay, alumina, sand, Al2O3, Fe2O3, also can together heat with the Cl2-S compound.Handle the phosphorus ore of different mass in different ways, in various conditions and equipment design, element is converted into required product mix.

Can also find; The inventive method can use the carbonaceous thing (for example inferior grade coke or semicoke) of minimum quantity (only to decompose as heating energy source in process of production; Do not waste reductive agent); Through the phosphorus ore of direct processing different mass, avoid the use of direct electric energy and carry out phosphorus and phosphorus derivant and Cement Production.

Can also find: compared to already known processes of the prior art, that the inventive method needs is a small amount of (as only 30%) silicon-dioxide and/or aluminum oxide mix with phosphorus ore to obtain to use always cement.

In the methods of the invention, through using the inferior grade coke but not use a large amount of electric energy, directly handle the phosphorus ore of different mass and produce phosphorus and phosphorus derivant, utilized heat energy efficiently, thereby heat release and thermo-negative reaction obtain balance to a great extent.

The inventive method uses the mode that other elements beyond the phosphoric are converted into cement clinker that the phosphorus ore of different mass is handled fully; Produce in view of the above at commercial significant cement commonly used and phosphorus chloride and phosphorus derivant, in fact this from having eliminated a large amount of wastes.

Summary of the invention

With calcium phosphate or any its source (phosphorus ore that for example contains 2% to 45% any per-cent phosphorus; The phosphorus ore that contains 25-40% phosphorus (as P2O5) of preferred report usually) grinds to form fine powder (between 20 to 150 orders; 60-100 order preferably); With the compound of desired number (for example the SiO2 of respective pure form, Fe2O3, A12O3 or any wherein one or more, perhaps consider economic cause, the clay of preferred mineral forms, alumina, flying dust, sand etc.) mix.Preferably all materials are ground to form fine grain size, carry out thorough mixing; And at first heat with the temperature of 1100 ℃ to 1300 ℃ (preferred 1200 ℃ to 1400 ℃) at this point, or after carrying out prilling or micronize or process piece with any method well known in the prior art again with the temperature heating of 1100 ℃ to 1300 ℃ (preferred 1200 ℃ to 1400 ℃).This heating possibly receive the influence of electric arc, resistance-type heating, preferred gas or air or any carbonaceous thing of oxygen-rich air (preferably near purity oxygen) burning that contains O2 (pure O2) that use.

Moisture in the reaction process or moisture are deleterious to the generation of numerous high value products, therefore, should through heating and/or calcining all input materials moisture or moisture be remained on minimum quantity according to currently known methods of the prior art.

As another embodiment of the inventive method, the phosphorus that produces in first reaction and other products of gaseous form condense for part or coagulation forms fully, can with other separating substances; After guaranteeing fully to remove phosphorus content and in cement, forming suitable mineral facies, can cement be screened from solid part.

In another embodiment; Further with the product of the phosphorous and oxide compound of fs and carbonaceous thing (preferred CO) with chlorine (compound that comprises its reactant (such as Cl2 itself), COCl2, any sulfur subchloride or sulphur and chlorine) generation partially or completely react, generate the muriate of any or all phosphorus and/or sulphur.Condensation and/or the purification in appropriate solvent (for example Benzene Chloride, dichlorobenzene etc.) of these muriates.Select suitable reactant, high value chemical (for example phosphorus, PCl3, P2O5, P2S5 and phosphoric acid etc.) uses method well known in the prior art to separate.

Can use suitable treatment process well known in the prior art that any unwanted element or compound (for example CaF2) are reverted to the level that can make us accepting, for example discharge with the HF form through heated moisture.

According to the present invention; In Powdered ore and any type of fine-grannular or disintegrated SiO2, A12O3, Fe2O3 or any wherein a kind of adding fluidized-bed reactor, fixed-bed reactor, shaft furnace or rotary kiln (so long as known suitable type gets final product in the chemical engineering technology); Preferably between 1500 ℃, react at 1200 ℃; When using cement always so that other elements except phosphoric that exist in the phosphorus ore are converted into, phosphoric will directly discharge and subsequent transformation is a phosphorus derivant.

The main chemical reactions that takes place includes but not limited to following:

1.P2O5+5CO+3Cl2→2PCl3+5CO2

2.CO2+3C+O2→4CO.

3.P+3/2Cl2→PCl3

4.PCl3+Cl2→PCl5.

5.Ca3(PO4)2+x?SiO2+y?Al2O3+z?Fe2O3→3CaO.xSiO2.y?Al2O3.z?Fe2O3+P2O5

This is the method for the formation cement of extreme simplification really.Actual mineral facies are complicated more, and this has very detailed description in cement production technology and science.Certainly, can add other mineral, obtain having the cement of special characteristics through the simple extension same process.

6.Ca3(PO4)2+ 5C→3CaO+5CO+2P.

7.C+O2→CO2.

8.2CO+O2→2CO2

9.CO+CL2→COCl2.

Embodiment

Embodiment 1

Raw mix comprises 100 parts of rock phosphates, 10 parts of silica sands, 6 parts of clays and 28.6 parts of coke (mol ratio of CaO: SiO2 is 3: 1).Rock Phosphate (72Min BPL) decomposites 33.68% P2O5,45.90% CaO, 4.9% SiO2,0.56% Al2O3 and 3.43% Fe2O3 (by weight), in ball mill, polish (through 200 order meshes).The coke that uses has low volatility, it is ground to-200 orders size.The river silica sand that will contain 82%SiO2 simultaneously is ground to-200 orders size and mixes with rock phosphate-carbon mixture.Mixture is poured in the vibration nodulizer.Congeries adding external diameter with 50gms after 800 ℃ are calcined 2 hours is that 48mm, internal diameter are that 40mm, length are in the alumina tube reactor drum of 375mm.Through electrically heated alumina reactor is heated to 1050 ℃ at first, temperature is raise and maintain 1300 ℃ to 1400 ℃ through burning bed coke 4 hours in oxygen then.The gaseous product that contains P2O5 through Powdered semicoke fluidized-bed, is converted into PCl3 (keep reactor cooling, with temperature maintenance about 600 ℃-700 ℃) with excessive a little Cl2, uses the glass holding tank of externally cooled to collect the product of this reactor drum.Product liquid is mainly PCl3, and secondary product is some PCl5 that superfluous Cl2 produces.

The grog residue of after reaction finishes, collecting contains 2.4%P ₂O ₅(corresponding 94.2% removal amount).

Embodiment 2

The initial raw material mixture is processed through the congeries (mol ratio of CaO and SiO2 equals 2: 1) that mix above-mentioned raw materials and CaO and SiO2.In the raw material congeries, add 21.5 parts of semicokes (mol ratio that is equivalent to P2O5 and carbon is 1: 10).At first with reaction bed through being electrically heated to 1000 ℃, in the reaction bed that contains the raw material congeries, charge into O2 then, temperature is elevated to 1250 ℃.In the exit of Gas-phase reactor product gas is mixed with chlorine then.Final product is a fuming liquid, uses refrigerative glass-lined jar to collect.Analyze the phosphorus and the cl content of product liquid, find to contain the little fluid drips of PCl3 and some phosphorus containg substances.

Analyze the residue P2O5 of grog residue, confirm to have about 90% P2O5 removal amount.Resistates also contains 5% unreacted carbon, and it has stoped the congeries fusing, has facilitated maximum P2O5 clearance.

Embodiment 3

Raw mix comprises 100 parts of rock phosphates, 51 parts of silica sands (mol ratio of CaO: SiO2 is 1: 1) and 40 parts of coke.Rock Phosphate (72Min BPL) decomposites 33.68% P2O5,45.90% CaO, 4.9% SiO2,0.56% Al2O3 and 3.43% Fe2O3 (by weight), in ball mill, polish (through 200 order meshes).The coke that uses has low volatility, it is ground to-200 orders size.Simultaneously the river silica sand is ground to-200 orders sizes and mixes with rock phosphate-carbon mixture.The mixture that mixes is poured in the vibration nodulizer.Congeries adding external diameter with 50gms after 800 ℃ are calcined 2 hours is that 48mm, internal diameter are that 40mm, length are in the alumina tube reactor drum of 375mm.Through electrically heated alumina reactor is heated to 1050 ℃ at first, temperature is raise and maintain 1300 ℃ to 1400 ℃ through burning bed coke 4 hours in oxygen then.The gaseous product that contains P2O5 passes through Powdered semicoke fluidized-bed with excessive a little Cl2, is converted into PCl3, uses the product of this reactor drum of glass holding tank collection of externally cooled.Product liquid is mainly PCl3, also has some PCl5.

In the cohesiveness Calucium Silicate powder, the grog residue of after reaction finishes, collecting contains 2.4%P2O5 (corresponding 94.2% removal amount).

Embodiment 4

Get 50 parts of rock phosphates, 24.5 parts of silica sands (mol ratio of CaO: SiO2 is 1: 1), 13 parts of low volatility coke and prepare raw mix, and saidly grind respectively according to top.Mixture after thoroughly kneading grinds carries out single gathering, and is reinforced to reactor drum.Rock Phosphate (72Min BPL) decomposites 33.68% P2O5,45.90% CaO, 4.9% SiO2,0.56% Al2O3 and 3.43% Fe2O3 (by weight); In ball mill, polish in (through 200 order meshes).The coke that uses has low volatility, it is ground to-200 orders size.Simultaneously the river silica sand is ground to-200 orders sizes and mixes with rock phosphate-carbon mixture.The mixture that mixes is poured in the vibration nodulizer.Congeries adding external diameter with 50gms after 800 ℃ are calcined 2 hours is that 48mm, internal diameter are that 40mm, length are in the alumina tube reactor drum of 375mm.Through electrically heated alumina reactor is heated to 1050 ℃ at first, temperature is raise and maintain 1200 ℃ to 1250 ℃ through burning bed coke 4 hours in oxygen then.The gaseous product and the Cl2 stream that will contain P2O5 together pass through fluidized-bed.Use the glass-lined jar of externally cooled to collect green fuming liquid.Product is analyzed discovery, and it contains PCl3 and some as PCl5, POCl3 and P2O5 that impurity occurs, can separate through already known processes of the prior art.

In the cohesiveness Calucium Silicate powder, the grog residue of after reaction finishes, collecting contains P2O5 less than 2% (1.90%P2O5 corresponding to about 96% P2O5 removal amount).

Embodiment 5

From the product waste gas (containing P2O5 and P4 and CO) of first reactor drum and chlorine (chlorine and P2O5 mol ratio are 3: 1) when in Gas-phase reactor, carrying out 700 ℃; The fluidized-bed reactor that contains the carbon bed can promote chloridization process, and under the situation that only consumes stoichiometry chlorine, realizes maximize production.

Advantage:

1, the inventive method is only added a small amount of coke and oxygen, but balance heat release and thermo-negative reaction.

2, practice thrift operation cost and cost of capital.

3, in the prior art, the sub product great majority are Calucium Silicate powder, and what the inventive method was different with it is: sub product is merely cement clinker.Therefore can realize more high value and utilization ratio.

4, there is the less shortcoming of product flexibility in prior art, and the inventive method can produce multiple phosphorus derivant.

5, have technology integration and handiness, practice thrift cost of capital.

Claims (according to the modification of the 19th of treaty)

1. one kind prepares phosphorus trichloride, phosphorus pentachloride and cement; Preferably the method for silicate cement is characterized in that, comprising: use 1100 ℃ to 1500 ℃ heat to contain the phosphorus ore powder mixture of quicklime, carbonaceous thing, silicon-dioxide and/or aluminum oxide; Wherein the ratio of quicklime and silicon-dioxide be 1.4 or more than; Use chlorine to handle the synthesis gas product, through cooling temperature is remained on 400 ℃ to 1000 ℃ simultaneously, wherein the mol ratio of contained phosphorous oxides is 1: 5 in chlorine and the phosphorus ore; Thereafter; The gaseous mixture that at first will mainly contain phosphorus trichloride and phosphorous pentachloride separates with cement commonly used, secondly phosphorus trichloride is separated with phosphorous pentachloride, and twice separation all adopts currently known methods to carry out.

The method of claim 1, wherein carbonaceousmaterial be following one or more: coke, semicoke, pitch, charcoal or biomass C.

3. according to claim 1 or claim 2 method is characterized in that phosphorus ore contains 2% to 45% phosphorous oxides.

4. like claim 1 or 2 or 3 described methods, it is characterized in that,, use chlorine that synthetic gaseous product is handled in the ratio of 1 mole of phosphorous oxides to 3 moles of chlorine.

5. require described method as claim 1 to 4 is arbitrary, it is characterized in that, the heat to 1200 of phosphorus ore, carbonaceousmaterial, silicon-dioxide and/or aluminum oxide ℃ temperature to 1400 ℃.

6. require described method as claim 1 to 5 is arbitrary, it is characterized in that, in phosphorus ore, carbonaceousmaterial, silicon-dioxide and/or alumina mixture, add red stone, and said mixture has been worn into powder.

7. require described method as claim 1 to 6 is arbitrary, it is characterized in that, when using chlorine to handle the synthesis gas product, temperature remains on 500 ℃ to 700 ℃.

Explain or state (according to the modification of the 19th of treaty)

Revised comment according to the 19th of Patent Cooperation Treaty

Explanation

Brief introduction part of the present invention is clear to be pointed out, the present invention relates to the technology of a kind of production " cement commonly used such as silicate cement ".The ratio of quicklime and silicon-dioxide must not be less than 1 in the cement commonly used; This ratio must not be less than 1.4 in the silicate cement.The present invention is intended to produce cement commonly used (preferably silicate cement), phosphorus trichloride and phosphorus pentachloride, but this point clear pointing out in claim 1.Therefore, claim 1 need be made amendment, and illustrates characteristics of the present invention with clear, and it is distinguished with prior art mutually.

In view of the remarks (2.1) in International Searching Authority's written comment, cancel/delete claim 8 as blanket.

Influence:

Request is suitably revised the present invention's general introduction, and itself and the claim of having revised 1 are consistent.Summary of the invention also will be made amendment, and adds the minimum proportion of quicklime and silicon-dioxide therein.Embodiment 3 and 4 should delete.

Claims

1. method for preparing phosphorus trichloride, phosphorous pentachloride and cement commonly used; It is characterized in that, comprising: use the powder mixture of 1100 ℃ to 1500 ℃ heat phosphorus ore, carbonaceous thing, silicon-dioxide and/or aluminum oxide, use chlorine to handle the synthesis gas product; Through cooling temperature is remained on 400 ℃ to 1000 ℃ simultaneously; Wherein the mol ratio of contained phosphorous oxides is 1: 5 in chlorine and the phosphorus ore, and thereafter, the gaseous mixture that at first will mainly contain phosphorus trichloride and phosphorous pentachloride separates with cement; Secondly phosphorus trichloride is separated with phosphorous pentachloride, twice separation all adopts currently known methods to carry out.

2. the method for claim 1 is characterized in that, the carbonaceous thing be following one or more: coke, semicoke, pitch, charcoal or biomass C.

5. require described method as claim 1 to 4 is arbitrary, it is characterized in that, the heat to 1200 of phosphorus ore, carbonaceous thing, silicon-dioxide and/or aluminum oxide ℃ temperature to 1400 ℃.

6. require described method as claim 1 to 5 is arbitrary, it is characterized in that, in phosphorus ore, carbonaceous thing, silicon-dioxide and/or alumina mixture, add red stone, and said mixture has been worn into powder.

8. a method for preparing phosphorus trichloride, phosphorous pentachloride and cement is referring to described herein and embodiment.